CN110212159A - A kind of composite negative pole pole piece and preparation method thereof - Google Patents
A kind of composite negative pole pole piece and preparation method thereof Download PDFInfo
- Publication number
- CN110212159A CN110212159A CN201910518641.9A CN201910518641A CN110212159A CN 110212159 A CN110212159 A CN 110212159A CN 201910518641 A CN201910518641 A CN 201910518641A CN 110212159 A CN110212159 A CN 110212159A
- Authority
- CN
- China
- Prior art keywords
- cathode
- coating
- pole piece
- water
- soluble
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A kind of composite negative pole pole piece and preparation method thereof, belongs to field of power lithium ion battery technology.The cathode coating includes cathode coated inside and negative outer coating, the cathode coated inside coating is on a current collector, the negative outer coating is coated on cathode coated inside, and the cathode coated inside is water-soluble coating, and the negative outer coating is oil-soluble coating.Advantages of the present invention are as follows: coat one layer of lithium titanate material in traditional graphite cathode coating, the first effect of battery can be improved, and then improve the mass-energy density metric density of battery；Improve fast charge ability, cycle life and the security performance of battery.
Description
Technical field
The invention belongs to field of power lithium ion battery technology, and in particular to a kind of composite negative pole pole piece and its preparation side
Method.
Background technique
It is universal with New-energy electric vehicle application, cruising ability of the people to New-energy electric vehicle, quick charge
Ability and security performance propose increasingly higher demands.The negative electrode material of current driving force lithium ion battery is mainly graphite-like
Material is easy to analysis lithium in cyclic process, causes cycle life since its intercalation potential is in the left and right 0.1V (VS.Li)
It is low, and it is easy to happen safety accident.Meanwhile conventional anode graphite is two-dimensional layered structure, interlamellar spacing 0.335nm is lesser
Interlamellar spacing makes the diffusion rate of lithium ion lower, and high rate performance is poor.Under conditions of quick charge, lithium ion is easily in graphite
Surface deposits to form Li dendrite.With the increase of cycle-index, the continuous growth of battery capacity rapid decay, and Li dendrite can be pierced
It wears diaphragm and causes internal short-circuit of battery, eventually lead to safety accident.
In order to improve the fast charge ability of power battery, conventional method is the active material load by reducing positive/negative plate
Amount carries out cladding hard carbon in carbon material surface to reach the fast charge ability for improving lithium ion battery, but will cause lithium ion battery
Energy density decline, while in cyclic process side reaction cause its cycle life decline.
Summary of the invention
The problem of declining the purpose of the present invention is to solve lithium ion battery energy density and cycle life, provides one kind
With high safety fast charging type Power compound cathode pole piece and preparation method thereof, this method passes through using the double-deck coating technique, negative
Pole surface coats one layer of lithium titanate (LTO) coating.Since LTO has good rapid charging performance, security performance, finally make
The fast charge ability and security performance of battery are effectively improved.
To achieve the above object, the technical solution adopted by the present invention is as follows:
A kind of composite negative pole pole piece, including collector and cathode coating, the cathode coating include cathode coated inside and
Negative outer coating, on a current collector, the negative outer coating is coated in inside cathode and applies for the cathode coated inside coating
On layer, the cathode coated inside is water-soluble coating, and the negative outer coating is oil-soluble coating.
Further, the cathode coated inside by negative electrode active material 1, water-soluble binder, water-soluble thickener, lead
Electric agent is prepared；The negative electrode active material 1: water-soluble binder: water-soluble thickener: the mass percent of conductive agent is
80.0%~98.0%:0.2%~10.0%:0.2%~10.0%:0%~8.0%.
Further, the negative outer coating is prepared by negative electrode active material 2, oil-soluble binder, conductive agent；
The negative electrode active material 2, oil-soluble binder, conductive agent mass percent be 80.0%~98.0%:0.1%~
15.0%:0.1%~10.0%.
A kind of preparation method of above-mentioned composite negative pole pole piece, the method comprises the following steps:
Step 1: negative electrode active material 1, conductive agent are mixed into 0.5~8h, obtain uniformly mixed dry powder；It is added 15%
~75% water-soluble thickener stirs 1~30min, makes slurry in dough, then proceedes to 0.5~8h of stirring, makes slurry point
It dissipates uniform；Water-soluble binder is added and remaining water-soluble thickener stirs 0.5~10h, is completely dispersed slurry uniformly；Most
After vacuumize removing bubble, cathode internal layer slurry is obtained after the screen to filtrate using 100~300 mesh；
Step 2: the cathode internal layer slurry that step 1 obtains is uniformly coated on collector, in an oven in 30 DEG C
~200 DEG C of 0.1~30min of heated baking make the partial solvent water in cathode internal layer slurry volatilize, it is desirable that and pole piece cannot be dried and be split,
Pole piece cannot cause roll banding due to overly wet simultaneously, the collector coated with cathode internal layer slurry be obtained, at 25 DEG C~180 DEG C
Dry 0.5~12h, obtains the pole piece of coating cathode coated inside；
Step 3: oil-soluble binder, dispersant are stirred into 0.5~10h, make oil-soluble binder completely homogeneously
Dispersion；Conductive agent is added, 0.5~8h is mixed, so that conductive agent is completely dispersed uniformly；The mixing of negative electrode active material 2 is added to stir
0.5~15h is mixed, so that negative electrode active material 2 is completely dispersed uniformly；Removing bubble is finally vacuumized, 100~300 purposes are used
Sieve is filtered slurry, obtains cathode outer layer slurry；
Step 4: the cathode outer layer slurry that step 3 obtains is uniformly coated on the cathode coated inside that step 2 obtains
On, in an oven in 30 DEG C~200 DEG C progress 0.1~40min of heated baking, the dispersing agent in slurry is made to volatilize completely；It will be double
The negative electrode tab of layer coating at 25 DEG C~180 DEG C dry 0.5~12h, roll-in to get arriving composite negative pole pole piece.
The present invention having the beneficial effect that compared with the existing technology
(1) one layer of lithium titanate material is coated in traditional graphite cathode coating, and the first effect of battery, Jin Erti can be improved
The mass-energy density metric density of high battery；
(2) fast charge ability, cycle life and the security performance of battery are improved.
Detailed description of the invention
Fig. 1 is the double-deck coating negative electrode tab schematic diagram.
Specific embodiment
Further description of the technical solution of the present invention with reference to the accompanying drawings and embodiments, and however, it is not limited to this,
All to be modified to technical solution of the present invention or equivalent replacement, range without departing from the spirit of the technical scheme of the invention should all
Cover within the protection scope of the present invention.
Specific embodiment 1: present embodiment record is a kind of composite negative pole pole piece, including collector and cathode apply
Layer, as shown in Figure 1, the cathode coating includes cathode coated inside and negative outer coating, the cathode coated inside coating
On a current collector, the negative outer coating is coated on cathode coated inside, and the cathode coated inside is water-soluble coating,
The negative outer coating is oil-soluble coating.
Specific embodiment 2: a kind of composite negative pole pole piece described in specific embodiment one, the cathode coated inside
It is prepared by negative electrode active material 1, water-soluble binder, water-soluble thickener, conductive agent；The negative electrode active material 1: water
Soluble binder: water-soluble thickener: the mass percent of conductive agent is 80.0%~98.0%:0.2%~10.0%:
0.2%~10.0%:0%~8.0%.
Specific embodiment 3: a kind of composite negative pole pole piece described in specific embodiment two, the negative electrode active material 1
For one of artificial graphite, natural graphite, soft carbon, hard carbon, carbonaceous mesophase spherules (MCMB) or a variety of combinations；It is described water-soluble
Property binder be acrylic acid and acrylic ester copolymers, polyacrylamide, polyethylene glycol oxide, polyvinylpyrrolidone, acryloyl
Amine-acrylonitrile copolymer, acrylic acid-acrylamide-acrylonitrile copolymer, in acrylic acid-acrylic ester-acrylonitrile copolymer
One or more combinations；The water-soluble thickener is sodium carboxymethylcellulose (CMC), hydroxyethyl cellulose, hydroxypropyl are fine
Tie up element, diutan, polyvinyl alcohol, combination one or more in polyacrylic acid；The conductive agent is electrically conductive graphite, conductive black
(Super-P), one of Ketjen black, acetylene black, carbon fiber, single-walled carbon nanotube, multi-walled carbon nanotube, graphene or a variety of
Group；.
Specific embodiment 4: a kind of composite negative pole pole piece described in specific embodiment one, the negative outer coating
It is prepared by negative electrode active material 2, oil-soluble binder, conductive agent；The negative electrode active material 2, is led at oil-soluble binder
The mass percent of electric agent is 80.0%~98.0%:0.1%~15.0%:0.1%~10.0%.
Specific embodiment 5: a kind of composite negative pole pole piece described in specific embodiment four, the negative electrode active material 2
For lithium titanate；The oil-soluble binder is to gather inclined tetrafluoroethene；The conductive agent be electrically conductive graphite, conductive black, Ketjen black,
One of acetylene black, carbon fiber, single-walled carbon nanotube, multi-walled carbon nanotube, graphene or a variety of combinations.Present invention optimization
The coating method of lithium ion power cell cathode pole piece is improved, especially in one layer of lithium titanate of ordinary graphite cathode applied atop
Coating improves the first charge discharge efficiency of battery, while can play and inhibit SEI of the ordinary graphite cathode in continuous charge and discharge process not
It is disconnected to decompose the loss for generating and causing active lithium, and then improve the cycle life of battery.Meanwhile LTO coating can significantly improve
The security performance of traditional lithium-ion battery.
Specific embodiment 6: composite negative pole pole piece described in a kind of any specific embodiment of specific embodiment one to five
Preparation method, the method comprises the following steps:
Step 1: negative electrode active material 1, conductive agent are mixed into 0.5~8h, obtain uniformly mixed dry powder；It is added 15%
~75% water-soluble thickener stirs 1~30min, makes slurry in dough, then proceedes to 0.5~8h of stirring, makes slurry point
It dissipates uniform；Water-soluble binder is added and remaining water-soluble thickener stirs 0.5~10h, is completely dispersed slurry uniformly；Most
After vacuumize removing bubble, cathode internal layer slurry is obtained after the screen to filtrate using 100~300 mesh；
Step 2: the cathode internal layer slurry that step 1 obtains is uniformly coated on collector, in an oven in 30 DEG C
~200 DEG C of 0.1~30min of heated baking make the partial solvent water in cathode internal layer slurry volatilize, it is desirable that and pole piece cannot be dried and be split,
Pole piece cannot cause roll banding due to overly wet simultaneously, the collector coated with cathode internal layer slurry be obtained, at 25 DEG C~180 DEG C
Dry 0.5~12h, obtains the pole piece of coating cathode coated inside；Water-soluble thickener is neutral or slant acidity solution；It has coated
It is split when crossing baking oven in order to prevent pole piece baking, pole piece is not completely dried, and is needed after having coated dry so that remaining moisture
Volatilization；
Step 3: oil-soluble binder, dispersant are stirred into 0.5~10h, make oil-soluble binder completely homogeneously
Dispersion；Conductive agent is added, 0.5~8h is mixed, so that conductive agent is completely dispersed uniformly；The mixing of negative electrode active material 2 is added to stir
0.5~15h is mixed, so that negative electrode active material 2 is completely dispersed uniformly；Removing bubble is finally vacuumized, 100~300 purposes are used
Sieve is filtered slurry, obtains cathode outer layer slurry；
Step 4: the cathode outer layer slurry that step 3 obtains is uniformly coated on the cathode coated inside that step 2 obtains
On, in an oven in 30 DEG C~200 DEG C progress 0.1~40min of heated baking, the dispersing agent in slurry is made to volatilize completely；It will be double
(compacted density is 1.2~2.0g/cm to the negative electrode tab of layer coating for dry 0.5~12h, roll-in at 25 DEG C~180 DEG C3) to get
To composite negative pole pole piece.It was split when having coated baking oven in order to prevent pole piece baking, pole piece is not completely dried, and is needed after having coated
It dries so that remaining moisture evaporation.
Specific embodiment 7: a kind of preparation method of composite negative pole pole piece, step 1 described in specific embodiment six
In, the solid content of the cathode internal layer slurry is 20%~85%, and viscosity is 400~9000mPas.The solid content is consolidated
Body refers to that negative electrode active material 1, conductive agent, water-soluble thickener and water-soluble binder, liquid refer to the water of dispersed paste, be not required to
To add other solvent again.
Specific embodiment 8: a kind of preparation method of composite negative pole pole piece, step 2 described in specific embodiment six
In, the cathode coated inside with a thickness of 20~200um, surface density is 10~250g/m2。
Specific embodiment 9: a kind of preparation method of composite negative pole pole piece, step 3 described in specific embodiment six
In, the solid content of the cathode outer layer slurry is 20%~85%, and viscosity is 2000~15000mPas.The amount master of dispersing agent
If being contained admittedly according to the slurry of design to be added, containing admittedly for slurry is 20%~85%, then the amount of dispersing agent is 15%~80%；
The dispersing agent is N-Methyl pyrrolidone.The solid of the solid content refers to negative electrode active material 2, conductive agent and water-soluble bonding
Agent, liquid refer to the oil-soluble dispersant (N-Methyl pyrrolidone) of dispersed paste, do not need to add other solvent again.
Specific embodiment 10: a kind of preparation method of composite negative pole pole piece, step 4 described in specific embodiment six
In, the negative outer coating with a thickness of 20~100um, surface density is 10~200g/m2。
Embodiment 1
A kind of composite negative pole pole piece, the composite negative pole pole piece are the cathode pole piece of the double-deck coated structure, including collector,
Cathode coated inside and negative outer coating, on a current collector, the negative outer coating applies for the cathode coated inside coating
It overlays on cathode coated inside, the cathode coated inside is water-soluble coating, and the negative outer coating is oil-soluble coating.
Further, the material of the cathode coated inside includes graphite negative electrodes active material, water-soluble binder, water
Soluble surfactant, conductive agent, the negative electrode active material are artificial graphite, and conductive agent is superconduction carbon black (Super-P), water-soluble
Thickener is sodium carboxymethylcellulose (CMC), and water-soluble binder is acrylic acid and acrylic ester copolymers.Wherein negative electrode active
Substance: conductive agent: water-soluble thickener: water-soluble binder mass percent is 94%:2.5%:2%:1.5%, acrylic acid
The ratio that monomer accounts for the water-soluble binder is 30%~40%, water-soluble preferable.
A kind of preparation method of above-mentioned composite negative pole pole piece, includes the following steps:
Step 1: artificial graphite, the superconduction carbon black dry powder that proportional quantity is added into double planetary mixer are mixed
1.5h；
Step 2: the water-soluble thickener of proportional quantity being added into agitator tank, adjusts additional proportion, makes slurry in dough
Shape continues to stir 2h；Then it is 4000~6000mPas that deionized water adjustment slurry viscosity, which is added, adds water-soluble bonding
Agent stirs 30min with the speed for the 15rpm that revolves；Continuously adding deionized water and adjusting final viscosity is 500~4000mPas,
It vacuumizes stirring 30min and obtains cathode internal layer slurry with the screen to filtrate of 200 mesh；
Cathode internal layer slurry: being applied to two surfaces of copper foil by step 3 with flush coater, then will coat cathode internal layer
The collector of slurry 0.1~30min of heated baking at a temperature of 30 DEG C~200 DEG C, makes the aqueous solvent in acidic aqueous solution volatilize,
Obtain the collector of coating cathode internal layer slurry coating；
Step 4: the collector for coating cathode internal layer slurry is placed in oven and dried, and oven temperature is 60~180 DEG C,
Baking time is 0.2~16h, and inflated with nitrogen is as protection gas in baking oven；The cathode coated inside with a thickness of 148um, face is close
Degree is 120g/m2；
Step 5: negative outer coating uses the formula of conventional oil system slurry, and the active material of cathode outer layer slurry is
Lithium titanate (Li4Ti5O12), conductive agent is Ketjen black, and oil-soluble binder, which uses, gathers inclined tetrafluoroethene (PVDF), the dispersing agent
Using N-Methyl pyrrolidone (NMP), active material Li4Ti5O12, Ketjen black, oil-soluble binder PVDF mass percent
For 93%:3.5%:3.5%.Oil-soluble binder, the dispersing agent stirring point of proportional quantity are added first in double-planet agitator tank
2~6h is dissipated, after oil-soluble binder is completely dispersed, the Ketjen black that proportional quantity is added into glue is dispersed with stirring 1~5h, then
The lithium titanate of proportional quantity is added in agitator tank and stirs 1~8h, adjusting slurry viscosity is 2000~15000mPas, is vacuumized
After stirring 10~120min, it is filtered with 200 mesh screens, obtains cathode outer layer slurry.Cathode outer layer slurry is coated in people
It makes above graphite water-base coated inside, is wound after 0.1~40min of heated baking at a temperature of 30 DEG C~200 DEG C by baking oven, so
The collector for coating cathode outer layer slurry is placed in 2~20h of baking in 60~150 DEG C of baking oven again afterwards, by cathode outer layer slurry
Dispersing agent volatilization completely, obtain coating negative outer coating collector, to after baking collector carry out roll-in, be compacted it is close
Degree is 1.0~2.0g/cm3, composite negative pole pole piece is made.
A kind of lithium ion battery containing above-mentioned composite negative pole pole piece, the lithium ion battery include above-mentioned composite negative pole pole
Piece, anode pole piece, diaphragm and electrolyte.
The preparation of anode pole piece: anode pole piece is prepared using conventional anode formula, positive material includes
LiNi0.5Co0.2Mn0.3O2, superconduction carbon black (Super-P), gather inclined tetrafluoroethene, by the above material be mixed anode sizing agent apply
It overlays on 6~25 μm of aluminium foil and dries, baking temperature is 60~150 DEG C, and baking time is 2~20h, and roll-in is compacted
Density is 3.0~4.0g/cm3Anode pole piece.
The preparation of lithium ion battery: using conventional electrolyte prescription, LiPF6As lithium salts, with ethylene carbonate (EC),
The mixture of propene carbonate (PC) and dimethyl carbonate (DMC) is solvent, adds electrolysis additive.
The diaphragm used is single side ceramics+two-sided oiliness LBG gluing diaphragm.
Battery core is made by lamination in anode pole piece, cathode pole piece, diaphragm, is encapsulated with aluminum plastic film, in the baking of nitrogen protection
In case, controlled at 60~180 DEG C, baking time is 2~56h, injects electrolyte, carries out the processes such as chemical conversion sorting, finally
Obtain the soft bag lithium ionic cell that capacity is 10Ah.
Embodiment 2
The present embodiment place different from embodiment 1 is: that negative electrode active material is selected in cathode coated inside is people
Make graphite: the mixing material of hard carbon=9:1 (mass ratio), remaining is same as Example 1.
Embodiment 3
The present embodiment place different from embodiment 1 is: that negative electrode active material is selected in cathode coated inside is people
The negative electrode material of one layer of hard carbon of Graphite Coating is made, remaining is same as Example 1.
Comparative example 1
The preparation process of this comparative example lithium ion battery is as follows:
(1) prepared by anode pole piece: anode uses the formula of conventional oil system slurry, and positive active material is
LiNi0.5Co0.2Mn0.3O2, conductive agent is superconduction carbon black (Super-P), and binder, which uses, gathers inclined tetrafluoroethene (PVDF), solvent
Using N-Methyl pyrrolidone (NMP), LiNi0.5Co0.2Mn0.3O2, Super-P and PVDF mass percent be 97%:
1.5%:1.5%.The LiNi of proportional quantity is added first in double-planet agitator tank0.5Co0.2Mn0.3O2And Super-P, with revolution
30rpm, rotation 1500rpm stir 10min, and the PVDF and a certain amount of NMP of proportional quantity are added into system, stir 2h, adjust
Slurry viscosity is 3000~12000mPa.s, after vacuumizing stirring 30min, is filtered with 200 mesh screens, and positive oil system is obtained
Slurry.Slurry is applied directly to collection liquid surface, by baking oven at a temperature of 30 DEG C~200 DEG C 0.1~30min of heated baking
After wind, then the collector for coating positive oil system slurry is placed in 100 DEG C of baking oven and toasts 8h, by point of positive oil system slurry
Powder volatilization completely, obtains the collector for coating positive coating, roll-in, compacted density 3.5g/cm is carried out after drying3, it is made
Anode pole piece.
(2) preparation of cathode pole piece: cathode pole piece is prepared using conventional cathode formula, cathode material includes artificial stone
Above several materials are mixed and made into negative electrode slurry, negative electrode slurry are coated on to 8 μm of copper foil by ink, Super-P, CMC and SBR
Upper drying, baking temperature is 100 DEG C, baking time 4h, and roll-in, and obtaining compacted density is 1.65g/cm3Cathode pole piece.
(3) preparation of lithium ion battery: using conventional electrolyte prescription, LiPF6As lithium salts, with ethylene carbonate
(EC), the mixture of propene carbonate (PC) and dimethyl carbonate (DMC) is solvent, adds electrolysis additive.It uses
Diaphragm is single side ceramics+two-sided oiliness LBG gluing diaphragm.Battery core is made by winding in anode pole piece, cathode pole piece, diaphragm,
It is encapsulated with aluminum plastic film, in the baking oven of nitrogen protection, 36h is toasted at 120 DEG C, injects electrolyte, carry out the processes such as chemical conversion sorting,
Finally obtain the soft bag lithium ionic cell that capacity is 5Ah.
The full battery that each embodiment is prepared carries out specific capacity and cycle performance test, the result of test are as follows:
First charge discharge efficiency, specific capacity and the loop-around data of 1 embodiment of table
From table 1 it follows that the full battery for using the composite negative pole pole piece of the method production in the present invention to be assembled into
The cathode pole piece of first charge discharge efficiency, circulation volume conservation rate, rapid charging performance and security performance than using conventional method to prepare
The full battery being assembled into is good.
Claims (10)
1. a kind of composite negative pole pole piece, including collector and cathode coating, it is characterised in that: the cathode coating includes in cathode
Portion's coating and negative outer coating, on a current collector, the negative outer coating is coated in negative for the cathode coated inside coating
On the coated inside of pole, the cathode coated inside is water-soluble coating, and the negative outer coating is oil-soluble coating.
2. a kind of composite negative pole pole piece according to claim 1, it is characterised in that: the cathode coated inside is lived by cathode
Property substance 1, water-soluble binder, water-soluble thickener, conductive agent are prepared；The negative electrode active material 1: water solubility bonding
Agent: water-soluble thickener: the mass percent of conductive agent be 80.0%~98.0%:0.2%~10.0%:0.2%~
10.0%:0%~8.0%.
3. a kind of composite negative pole pole piece according to claim 2, it is characterised in that: the negative electrode active material 1 is artificial
One of graphite, natural graphite, soft carbon, hard carbon, carbonaceous mesophase spherules or a variety of combinations；The water-soluble binder is third
Olefin(e) acid-acrylate copolymer, polyacrylamide, polyethylene glycol oxide, polyvinylpyrrolidone, the copolymerization of nitrile-acrylamide-acrylic acid nitrile
One of object, acrylic acid-acrylamide-acrylonitrile copolymer, acrylic acid-acrylic ester-acrylonitrile copolymer are a variety of
Combination；The water-soluble thickener is sodium carboxymethylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, diutan, polyethylene
One or more combination in alcohol, polyacrylic acid；The conductive agent is electrically conductive graphite, conductive black, Ketjen black, acetylene black, carbon
One of fiber, single-walled carbon nanotube, multi-walled carbon nanotube, graphene or a variety of combinations.
4. a kind of composite negative pole pole piece according to claim 1, it is characterised in that: the negative outer coating is lived by cathode
Property substance 2, oil-soluble binder, conductive agent are prepared；The matter of the negative electrode active material 2, oil-soluble binder, conductive agent
Amount percentage is 80.0%~98.0%:0.1%~15.0%:0.1%~10.0%.
5. a kind of composite negative pole pole piece according to claim 4, it is characterised in that: the negative electrode active material 2 is metatitanic acid
Lithium；The oil-soluble binder is to gather inclined tetrafluoroethene；The conductive agent is electrically conductive graphite, conductive black, Ketjen black, acetylene
One of black, carbon fiber, single-walled carbon nanotube, multi-walled carbon nanotube, graphene or a variety of combinations.
6. a kind of preparation method of composite negative pole pole piece described in Claims 1 to 5 any claim, it is characterised in that: described
Method and step is as follows:
Step 1: negative electrode active material 1, conductive agent are mixed into 0.5~8h, obtain uniformly mixed dry powder；Addition 15%~
75% water-soluble thickener stirs 1~30min, makes slurry in dough, then proceedes to 0.5~8h of stirring, disperse slurry
Uniformly；Water-soluble binder is added and remaining water-soluble thickener stirs 0.5~10h, is completely dispersed slurry uniformly；Finally
Removing bubble is vacuumized, cathode internal layer slurry is obtained after the screen to filtrate using 100~300 mesh；
Step 2: the cathode internal layer slurry that step 1 obtains is uniformly coated on collector, in an oven in 30 DEG C~200
DEG C 0.1~30min of heated baking, makes the partial solvent water in cathode internal layer slurry volatilize, it is desirable that pole piece cannot be dried and be split, while pole
Piece cannot cause roll banding due to overly wet, obtain the collector coated with cathode internal layer slurry, dry at 25 DEG C~180 DEG C
0.5~12h obtains the pole piece of coating cathode coated inside；
Step 3: oil-soluble binder, dispersant are stirred into 0.5~10h, divide oil-soluble binder completely homogeneously
It dissipates；Conductive agent is added, 0.5~8h is mixed, so that conductive agent is completely dispersed uniformly；Negative electrode active material 2 is added to be mixed
0.5~15h, so that negative electrode active material 2 is completely dispersed uniformly；Removing bubble is finally vacuumized, the sieve of 100~300 mesh is used
Net is filtered slurry, obtains cathode outer layer slurry；
Step 4: the cathode outer layer slurry that step 3 obtains is uniformly coated on the coated inside that step 2 obtains, is being dried
In 30 DEG C~200 DEG C progress 0.1~40min of heated baking in case, the dispersing agent in slurry is made to volatilize completely；By bilayer coating
Negative electrode tab at 25 DEG C~180 DEG C dry 0.5~12h, roll-in to get arriving composite negative pole pole piece.
7. a kind of preparation method of composite negative pole pole piece according to claim 6, it is characterised in that: described in step 1
The solid content of cathode internal layer slurry is 20%~85%, and viscosity is 400~9000mPas.
8. a kind of preparation method of composite negative pole pole piece according to claim 6, it is characterised in that: described in step 2
Cathode coated inside with a thickness of 20~200um, surface density is 10~250g/m2。
9. a kind of preparation method of composite negative pole pole piece according to claim 6, it is characterised in that: described in step 3
The solid content of cathode outer layer slurry is 20%~85%, and viscosity is 2000~15000mPas.
10. a kind of preparation method of composite negative pole pole piece according to claim 6, it is characterised in that: described in step 4
Negative outer coating with a thickness of 20~100um, surface density is 10~200g/m2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910518641.9A CN110212159A (en) | 2019-06-15 | 2019-06-15 | A kind of composite negative pole pole piece and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910518641.9A CN110212159A (en) | 2019-06-15 | 2019-06-15 | A kind of composite negative pole pole piece and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110212159A true CN110212159A (en) | 2019-09-06 |
Family
ID=67792866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910518641.9A Pending CN110212159A (en) | 2019-06-15 | 2019-06-15 | A kind of composite negative pole pole piece and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110212159A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111540880A (en) * | 2020-05-08 | 2020-08-14 | 珠海冠宇电池股份有限公司 | Negative plate, preparation method and lithium ion battery comprising negative plate |
| CN112952051A (en) * | 2019-12-11 | 2021-06-11 | 广州汽车集团股份有限公司 | Negative pole piece, preparation method of negative pole piece, lithium ion hard-package battery cell, lithium ion battery package and application of lithium ion hard-package battery cell |
| CN113388346A (en) * | 2021-06-03 | 2021-09-14 | 珠海冠宇电池股份有限公司 | Adhesive, electrode slurry with adhesive and lithium ion battery |
| CN114156437A (en) * | 2021-11-19 | 2022-03-08 | 浙江南都电源动力股份有限公司 | High-area-density lithium battery negative plate, preparation method and lithium battery |
| CN114388727A (en) * | 2020-10-21 | 2022-04-22 | 深圳格林德能源集团有限公司 | Thick negative pole piece and preparation method thereof |
| EP4020638A1 (en) * | 2020-12-22 | 2022-06-29 | Hansol Chemical Co., Ltd. | Anode slurry composition for secondary battery |
| WO2023142308A1 (en) * | 2022-01-27 | 2023-08-03 | 宁德时代新能源科技股份有限公司 | Negative electrode sheet, secondary battery, battery module, battery pack, and electrical device |
| CN117317234A (en) * | 2023-11-29 | 2023-12-29 | 瑞浦兰钧能源股份有限公司 | Silicon-based negative electrode slurry and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102332559A (en) * | 2010-07-12 | 2012-01-25 | 三洋电机株式会社 | Negative electrode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery |
| CN104956530A (en) * | 2014-01-06 | 2015-09-30 | 株式会社Lg化学 | Negative electrode for secondary battery and lithium secondary battery comprising same |
| US20160301095A1 (en) * | 2015-04-13 | 2016-10-13 | Corning Incorporated | High silica content substrate such as for use in thin-film battery |
| CN107732147A (en) * | 2017-11-24 | 2018-02-23 | 西安力能新能源科技有限公司 | A kind of lithium titanate battery cathode piece and preparation method thereof |
| CN108878893A (en) * | 2018-06-29 | 2018-11-23 | 桑顿新能源科技有限公司 | A kind of fast charge negative electrode of lithium ion battery modified collector and preparation method thereof |
| CN109585779A (en) * | 2018-10-30 | 2019-04-05 | 福建冠城瑞闽新能源科技有限公司 | Take into account the lithium ion cell electrode piece and preparation method of energy density and power density |
| CN109585780A (en) * | 2018-12-24 | 2019-04-05 | 珠海光宇电池有限公司 | A kind of anode composite pole piece and preparation method thereof and the lithium ion battery containing the pole piece |
-
2019
- 2019-06-15 CN CN201910518641.9A patent/CN110212159A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102332559A (en) * | 2010-07-12 | 2012-01-25 | 三洋电机株式会社 | Negative electrode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery |
| CN104956530A (en) * | 2014-01-06 | 2015-09-30 | 株式会社Lg化学 | Negative electrode for secondary battery and lithium secondary battery comprising same |
| US20160301095A1 (en) * | 2015-04-13 | 2016-10-13 | Corning Incorporated | High silica content substrate such as for use in thin-film battery |
| CN107732147A (en) * | 2017-11-24 | 2018-02-23 | 西安力能新能源科技有限公司 | A kind of lithium titanate battery cathode piece and preparation method thereof |
| CN108878893A (en) * | 2018-06-29 | 2018-11-23 | 桑顿新能源科技有限公司 | A kind of fast charge negative electrode of lithium ion battery modified collector and preparation method thereof |
| CN109585779A (en) * | 2018-10-30 | 2019-04-05 | 福建冠城瑞闽新能源科技有限公司 | Take into account the lithium ion cell electrode piece and preparation method of energy density and power density |
| CN109585780A (en) * | 2018-12-24 | 2019-04-05 | 珠海光宇电池有限公司 | A kind of anode composite pole piece and preparation method thereof and the lithium ion battery containing the pole piece |
Non-Patent Citations (1)
| Title |
|---|
| 吴宇平主编: "《锂离子电池应用与实践》", 31 January 2012 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112952051A (en) * | 2019-12-11 | 2021-06-11 | 广州汽车集团股份有限公司 | Negative pole piece, preparation method of negative pole piece, lithium ion hard-package battery cell, lithium ion battery package and application of lithium ion hard-package battery cell |
| CN111540880A (en) * | 2020-05-08 | 2020-08-14 | 珠海冠宇电池股份有限公司 | Negative plate, preparation method and lithium ion battery comprising negative plate |
| CN114388727A (en) * | 2020-10-21 | 2022-04-22 | 深圳格林德能源集团有限公司 | Thick negative pole piece and preparation method thereof |
| EP4020638A1 (en) * | 2020-12-22 | 2022-06-29 | Hansol Chemical Co., Ltd. | Anode slurry composition for secondary battery |
| CN113388346A (en) * | 2021-06-03 | 2021-09-14 | 珠海冠宇电池股份有限公司 | Adhesive, electrode slurry with adhesive and lithium ion battery |
| CN114156437A (en) * | 2021-11-19 | 2022-03-08 | 浙江南都电源动力股份有限公司 | High-area-density lithium battery negative plate, preparation method and lithium battery |
| WO2023142308A1 (en) * | 2022-01-27 | 2023-08-03 | 宁德时代新能源科技股份有限公司 | Negative electrode sheet, secondary battery, battery module, battery pack, and electrical device |
| CN117317234A (en) * | 2023-11-29 | 2023-12-29 | 瑞浦兰钧能源股份有限公司 | Silicon-based negative electrode slurry and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110212159A (en) | A kind of composite negative pole pole piece and preparation method thereof | |
| CN102544502B (en) | Anode and cathode conductive additive for secondary lithium battery, method for preparing conductive additive, and method for preparing secondary lithium battery | |
| CN102329538B (en) | Water-based conductive ink of a lithium-ion battery | |
| CN102694155B (en) | Silicon-carbon composite material, preparation method thereof and lithium ion battery employing same | |
| CN104008893B (en) | The preparation method of lithium ion hybrid capacitors and lithium ion hybrid capacitors thereof | |
| CN109585780A (en) | A kind of anode composite pole piece and preparation method thereof and the lithium ion battery containing the pole piece | |
| CN109585781A (en) | A kind of lithium ion battery negative electrode and the lithium ion battery using the pole piece | |
| CN103199258A (en) | Cathode material of lithium ion battery, preparation method of cathode, and lithium ion battery | |
| CN104600244A (en) | Multilayer positive plate, production method of positive plate and lithium ion battery | |
| CN101154750A (en) | High power gel polymer lithium ion power cell and method of producing the same | |
| CN109994722A (en) | A kind of Li1+xAlxTi2-x(PO3)4Cobalt acid lithium material of cladding and the preparation method and application thereof | |
| CN108493442A (en) | A kind of ternary lithium ion battery | |
| CN107482173A (en) | Lithium ion battery anode active material and preparation method thereof, anode plate for lithium ionic cell and lithium ion battery | |
| CN107749464A (en) | A kind of energy density lithium ion power battery | |
| CN113066960B (en) | Double-composite modified spinel lithium manganate positive plate and preparation method thereof | |
| CN103891030B (en) | Nonaqueous electrolytic solution secondary battery and utilization thereof | |
| CN107565117A (en) | A kind of silicon/composite cathode material of silicon/carbon/graphite and preparation method thereof | |
| CN110021755A (en) | A kind of sodium-ion battery | |
| CN103746100A (en) | V2O5 nanoparticle/graphene lithium ion battery positive pole material and preparation method thereof | |
| CN105551816A (en) | Positive plate of hybrid super capacitor and preparation method of positive plate and hybrid super capacitor | |
| CN110247013A (en) | Positive pole piece and electrochemical device containing same | |
| CN103682415A (en) | High-energy-density lithium ion battery and preparation technology thereof | |
| CN109859951A (en) | A kind of carbon-based composite negative pole material and preparation method thereof and a kind of electrochmical power source and preparation method thereof | |
| CN110112366A (en) | A kind of electrodes of lithium-ion batteries and lithium ion battery | |
| CN106340622A (en) | High-power high-energy chemical power supply and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 519180 No. 209 Pearl Peak Avenue, Jingan Town, Doumen District, Zhuhai City, Guangdong Province Applicant after: Zhuhai Guanyu Battery Co., Ltd Address before: 519180 No. 209 Pearl Peak Avenue, Jingan Town, Doumen District, Zhuhai City, Guangdong Province Applicant before: ZHUHAI COSLIGHT BATTERY Co.,Ltd. |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190906 |